CN116651456A - Biocompatible hydrogen evolution electrocatalyst and preparation method and application thereof - Google Patents

Biocompatible hydrogen evolution electrocatalyst and preparation method and application thereof Download PDF

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CN116651456A
CN116651456A CN202310527298.0A CN202310527298A CN116651456A CN 116651456 A CN116651456 A CN 116651456A CN 202310527298 A CN202310527298 A CN 202310527298A CN 116651456 A CN116651456 A CN 116651456A
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hydrogen evolution
evolution electrocatalyst
terephthalic acid
electrocatalyst
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李中坚
修思源
杨彬
侯阳
雷乐成
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Zhejiang University ZJU
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Abstract

The invention discloses a biocompatible hydrogen evolution electrocatalyst, a preparation method and application thereof, and belongs to the technical field of energy conversion and electrocatalysts, wherein the electrocatalyst comprises carbon nanotubes and metal nickel nanoparticles, and the metal nickel nanoparticles are wrapped in the carbon nanotubes with micropores and mesoporous structures; the preparation method comprises the following steps: respectively dissolving terephthalic acid and nickel acetate in N, N-dimethylformamide to obtain a terephthalic acid solution and a nickel acetate solution, dripping the nickel acetate solution into the terephthalic acid solution, heating, stirring, reacting, collecting a solid product, washing and drying to obtain the Ni-PTA metal organic framework; calcining the Ni-PTA metal organic framework at a high temperature under the inert gas atmosphere, cooling and then pickling to obtain the biocompatible hydrogen evolution electrocatalyst. The electrocatalyst has the advantages of low nickel ion dissolution and low active oxygen substance generation in neutral solution, has good biocompatibility, and can be applied to the electrocatalytic conversion of carbon dioxide by microorganisms.

Description

Biocompatible hydrogen evolution electrocatalyst and preparation method and application thereof
Technical Field
The invention relates to the technical field of energy conversion and electrocatalyst, in particular to a biocompatible hydrogen evolution electrocatalyst, a preparation method and application thereof.
Background
Microbial electrosynthesis is the utilization of electrical energy by microorganisms as a reducing power to CO 2 The process of reducing synthesis of glucose or other substrates into various chemicals, the system of which comprises an anode (counter electrode), a reference electrode and a cathode (working electrode), and the microbial electrosynthesis produces H by in situ electrolysis of water 2 And O 2 Providing electrons and energy for the growth and metabolism of the microorganism, and further utilizing the metabolic process of the microorganism to realize CO 2 High valued conversion of (2). In recent years, CO fixation by means of microbial electrosynthesis systems 2 The production of poly-beta-hydroxybutyrate, biofuels or a variety of complex multi-carbon products has become a current research hotspot. As a green sustainable biological carbon fixation technology, the technology not only can produce chemicals with high added value, but also can realize the CO as a greenhouse gas 2 Is fixed to provide CO 2 A platform for conversion to multi-carbon compounds.
Wild type copper greedy (Cupriavidus necator) has been extensively studied for use in CO as a typical carbon-fixing hydroxide microorganism 2 Conversion to biomass or poly-beta-hydroxybutyrate. Cupriavidus necator is taken as a chassis cell and is genetically modified to realize the following steps of CO 2 To the production of various biofuels such as isopropanol and isobutanol, and the synthesis of high value added products such as lycopene and alpha-humulone.
In addition, chinese patent publication No. CN107354478A discloses a method for reducing carbon dioxide at a cathode using mixed anaerobic microorganisms including probiotics, firmics and bacterioides, which can achieve reduction of carbon dioxide to volatile fatty acids using common electrode materials, and produce substances with high added value using a domesticated and enriched mixed bacteria system.
In order to make in-situ electrolytic water reaction more efficient in microorganism culture solution environment and improve electric energy conversion efficiency, the hydrogen evolution electrocatalyst is applied to a cathode of a microorganism electrosynthesis system and used for reducing overpotential of hydrogen evolution reaction. However, dissolution and accumulation of metallic elements in hydrogen evolution catalysts during electrocatalytic processes can inhibit the activity of carbon-fixing microorganisms. 25 mu mol L -1 Co of (C) 2+ And Ni 2+ Has obvious cytotoxicity. In addition, for aerobic microorganisms, by-product reactive oxygen species, including H, are produced by reduction of oxygen at the cathode 2 O 2 HO, etc., which destroy DNA, lipids, and proteins, affecting the metabolism and proliferation of microorganisms. Therefore, the biocompatibility of the cathodic hydrogen evolution electrocatalyst seriously affects the growth and metabolism of microorganisms in a microbial electrosynthesis system, thereby affecting CO 2 Conversion to high value added products. Therefore, designing a hydrogen evolution electrocatalyst capable of simultaneously reducing metal ion elution and ROS production with excellent biocompatibility is a problem that needs to be solved in the prior art.
Disclosure of Invention
The invention provides a biocompatible hydrogen evolution electrocatalyst, which comprises a carbon nano tube and metal nickel nano particles, wherein the metal nickel nano particles are wrapped in the carbon nano tube containing micropores and mesoporous structures; the electrocatalyst has a limited domain structure, can obviously reduce the dissolution of metallic nickel in the application process, reduces the generation of catalytic by-product Reactive Oxygen Species (ROS), and has excellent biocompatibility.
The technical scheme adopted is as follows:
a biocompatible hydrogen evolution electrocatalyst comprises 60-80wt% of carbon nanotubes and 20-40wt% of metallic nickel nanoparticles, wherein the metallic nickel nanoparticles are wrapped in the carbon nanotubes with micropores and mesoporous structures; preferably, the biocompatible hydrogen evolution electrocatalyst has micropores with a pore diameter of less than 3nm and mesopores with a pore diameter of 3-5 nm.
The biocompatible hydrogen evolution electrocatalyst provided by the invention has a specific structure, the metal nickel nano particles are wrapped in the carbon nano tubes, the electrocatalyst has a limited domain structure, the dissolution of metal nickel in the application process can be obviously reduced, the generation of catalytic by-product Reactive Oxygen Species (ROS) is reduced, the biocompatibility is excellent, and the electrocatalyst has a good application prospect in the electrocatalytic conversion of carbon dioxide by microorganisms.
The invention also provides a preparation method of the biocompatible hydrogen evolution electrocatalyst, which comprises the following steps:
(1) Respectively dissolving terephthalic acid and nickel acetate in N, N-dimethylformamide to obtain terephthalic acid solution and nickel acetate solution, dripping the nickel acetate solution into the terephthalic acid solution, heating, stirring, reacting, collecting solid products, washing and drying to obtain the Ni-PTA metal organic framework.
(2) Calcining the Ni-PTA metal organic frame obtained in the step (1) at a high temperature in an inert gas atmosphere, cooling to obtain black powder, and pickling to obtain the biocompatible hydrogen evolution electrocatalyst.
The invention takes nickel acetate as a nickel source and terephthalic acid as an organic ligand, firstly synthesizes a Ni-PTA metal organic framework, and further carries out calcination and acid washing operation on the framework to obtain the biocompatible hydrogen evolution electrocatalyst.
Preferably, in step (1), the concentration of the terephthalic acid solution is 0.1 to 0.3mol L -1 The method comprises the steps of carrying out a first treatment on the surface of the The concentration of the nickel acetate solution is 0.1-0.3mol L -1 The method comprises the steps of carrying out a first treatment on the surface of the The volume ratio of the terephthalic acid solution to the nickel acetate solution is 1:1-2.
Preferably, the conditions of the heating and stirring reaction are 80-120 ℃ for 2-8 hours.
Preferably, in the step (2), the inert gas atmosphere is nitrogen atmosphere, the calcination temperature is 700-900 ℃, and the calcination time is 2-3 hours. The calcination atmosphere, temperature and time influence the conductivity, specific surface area and dispersibility of nickel metal nano particles of the catalyst product, and under the preferable conditions, the activity of the obtained product catalyst for catalyzing hydrogen evolution reaction is higher.
Further preferably, the rate of temperature rise in the high-temperature calcination is 5 to 10℃for min -1 . The rate of temperature rise is too fast and will affect the formation of carbon nanotubes.
Preferably, in step (2), 0.5mol L is used -1 The pickling time is 12-24 h. Under the above-mentioned preferable acid washing conditions, metallic nickel nanoparticles exposed outside the carbon nanotubes can be sufficiently removed.
The invention also discloses application of the biocompatible hydrogen evolution electrocatalyst in the electrocatalytic conversion of carbon dioxide by microorganisms, preferably a microbial electrosynthesis system, the biocompatible hydrogen evolution electrocatalyst is loaded on a cathode, the overpotential of the cathodic hydrogen evolution reaction is reduced, and the fixation of CO by aerobic microorganisms or anaerobic microorganisms is promoted 2 And converts it into high value-added products such as poly-beta-hydroxybutyrate and the like.
The invention also provides a method for converting carbon dioxide by using the microorganism electrocatalytic reaction, which comprises the following steps: constructing a three-electrode system, taking a carbon electrode carrying the biocompatible hydrogen evolution electrocatalyst as a cathode, ag/AgCl as a reference electrode, a platinum electrode as an anode, forming a closed loop by the cathode, the reference electrode, the anode and an electrochemical workstation, taking an aerobic microorganism culture solution as electrolyte, connecting the electrochemical workstation, inoculating aerobic microorganisms, and controlling the OD of the electrolyte during initial inoculation 600 Is 0.2 to 0.3, and is operated at a cathode voltage of minus 0.9 to minus 1.2V (relative to a saturated silver/silver chloride electrode) at room temperature, CO is added 2 Converting into a high added value product.
Preferably, the aerobic microorganism is copper-pesticidal bacterium (Cupriavidus necator), and the electrolyte is a liquid culture solution of the copper-pesticidal bacterium known to those skilled in the art; the high added value product is poly beta-hydroxybutyrate. Experiments prove that the biocompatible hydrogen evolution electrocatalyst can realize good coupling with Cupriavidus necator in a microbial electrosynthesis system to realize CO 2 High value conversion to poly beta-hydroxybutyrate.
Compared with the prior art, the invention has the beneficial effects that:
(1) The biocompatible hydrogen evolution electrocatalyst provided by the invention has a specific structure, the biocompatible hydrogen evolution electrocatalyst comprises carbon nanotubes and metal nickel nanoparticles, the metal nickel nanoparticles are wrapped in the carbon nanotubes with micropores and mesoporous structures, and the limiting effect of the carbon nanotubes inhibits the dissolution of metal nickel, so that the electrocatalyst has the characteristic of low metal nickel ion dissolution, and further the cytotoxicity caused by metal ion dissolution is obviously reduced.
(2) When the biocompatible hydrogen evolution electrocatalyst is used for the electrocatalytic conversion of carbon dioxide by microorganisms, the biocompatible hydrogen evolution electrocatalyst has good hydrogen evolution performance in neutral microorganism culture solution, has stable catalysis time as long as 160 hours, has good catalysis performance and stability, and generates by-product active oxygen substances (such as H 2 O 2 HO, etc.), shows excellent biocompatibility, and has wide application prospect in the field of converting carbon dioxide by using the electrocatalytic microorganism.
Drawings
FIG. 1 is a graph showing pore size distribution of the biocompatible hydrogen evolution electrocatalyst prepared in example 1.
FIG. 2 is an SEM image of a biocompatible hydrogen evolution electrocatalyst prepared according to example 1.
FIG. 3 is a TEM image of the biocompatible hydrogen evolution electrocatalyst prepared in example 1.
FIG. 4 is a graph showing the polarization of an electrolytic water hydrogen evolution reaction in a microbial culture solution at a scan rate of 2mV s for the biocompatible hydrogen evolution electrocatalyst prepared in example 1 -1
FIG. 5 is a diagram showing H during the operation of the microbial electrosynthesis system of application example 1 2 O 2 Concentration build up graph over time.
FIG. 6 is a graph showing the accumulation of HO-concentration with time during the operation of the microbial electro-synthesis system of application example 1.
FIG. 7 is a graph showing the concentration of metal nickel ions eluted during the operation of the microbial electro-synthesis system of application example 2.
FIG. 8 is a graph showing the concentration of poly-beta-hydroxybutyrate produced from the electrocatalytic conversion of carbon dioxide by a microorganism in application example 3.
Detailed Description
The invention is further elucidated below in connection with the examples and the accompanying drawing. It is to be understood that these examples are for illustration of the invention only and are not intended to limit the scope of the invention. The methods of operation, under which specific conditions are not noted in the examples below, are generally in accordance with conventional conditions, or in accordance with the conditions recommended by the manufacturer.
The copper bacteria used in the examples (Cupriavidus necator) were purchased from the Beijing North Innova Biotechnology institute under the product number BNCC137386.
Example 1
(1) 0.332g of terephthalic acid was added to 10mL of N, N-dimethylformamide and stirred at 500rpm in an oil bath at 120℃until dissolved; 0.75g of nickel acetate tetrahydrate is weighed and put into 15mL of N, N-dimethylformamide, and dispersed by ultrasonic for 30min until dissolved; the concentrations obtained were 0.2mol L -1 A terephthalic acid solution and a nickel acetate solution; slowly dripping nickel acetate solution into terephthalic acid solution, continuously stirring the obtained mixed solution at 120 ℃ in an oil bath, centrifugally collecting pale green solid products after reacting for 8 hours, repeatedly washing with N, N-dimethylformamide, and drying in a 60 ℃ oven to obtain the Ni-PTA metal organic framework.
(2) Placing the obtained Ni-PTA metal organic frame in a tube furnace, and standing at 5deg.C for min under nitrogen atmosphere -1 Heating to 800 ℃ for calcination for 3 hours, and cooling to room temperature to obtain a black product; the black product was obtained with 0.5mol L -1 The sulfuric acid is pickled for 24 hours to obtain the biocompatible hydrogen evolution electrocatalyst.
Characterization of the biocompatible hydrogen evolution electrocatalyst shows that the content of metallic nickel in the biocompatible hydrogen evolution electrocatalyst is 30wt%, the average particle size of metallic nickel nano particles is 10-20nm, and the specific surface area of the biocompatible hydrogen evolution electrocatalyst is 162m 2 g -1 Pore volume of 0.53cm 3 g -1 . The pore size distribution results are shown in FIG. 1, and micropores with a diameter of less than 3nm and mesopores with a diameter of 3-5nm exist in the electrocatalyst.
The microstructure of the biocompatible hydrogen evolution electrocatalyst was observed by Scanning Electron Microscopy (SEM) and Transmission Electron Microscopy (TEM), respectively, as shown in fig. 2 and 3, it was seen that metallic nickel nanoparticles were encapsulated with carbon nanotubes. The metal nickel nano-particles regulate and control the electron cloud density of the carbon layer around the metal nickel nano-particles, and are used as active sites of the electrocatalyst for electrolytic water hydrogen evolution reaction in a neutral environment.
The hydrogen evolution performance of the electrocatalyst is measured by using a linear sweep voltammetry with a sweep rate of 2mV s by taking a microbial culture solution as an electrolyte -1 . As shown in the polarization graph of FIG. 4, the electrocatalyst had an overpotential of 444mV in the microorganism culture broth. Wherein the overpotential is that the current density is 10mA cm -2 The difference between the potential and the theoretical potential is measured. This result shows that the electrocatalyst has better electrocatalytic hydrogen evolution performance in microbial culture solution.
Example 2
In this example, the method for preparing the biocompatible hydrogen evolution electrocatalyst differs from that of example 1 only in that the concentration of terephthalic acid solution is 0.1mol L -1 The concentration of the nickel acetate solution is 0.1mol L -1 The method comprises the steps of carrying out a first treatment on the surface of the The reaction conditions were 80℃with stirring for 6h.
Example 3
In this example, the preparation method of the biocompatible hydrogen evolution electrocatalyst is different from that of example 1 only in that the high-temperature calcination temperature is 700 ℃, the calcination time is 2 hours, and the temperature rising rate is 10 ℃ for min -1 The pickling time is 12h.
Application example 1
The formula of the aerobic microorganism Cupriavidus necator culture solution is as follows: 9g L -1 Na 2 HPO 4 ·12H 2 O,1.5g L -1 KH 2 PO 4 ,0.2g L -1 (NH 4 ) 2 SO 4 ,80mg L -1 MgSO 4 ·7H 2 O,1mg L -1 CaSO 4 ·2H 2 O,50mg L -1 Ferric citrate, 200mg L -1 NaHCO 3 ,1.5mg L -1 NTA,0.3mg L -1 H 3 BO 3 ,0.2mg L -1 CoCl 2 ·6H 2 O,0.1mg L - 1 ZnSO 4 ·7H 2 O,0.03mg L -1 MnCl 2 ·4H 2 O,0.03mg L -1 Na 2 MoO 4 ·2H 2 O,0.02mg L -1 NiCl 2 ·6H 2 O,0.01mg L -1 CuSO 4 ·5H 2 O。
15mg of the biocompatible hydrogen evolution electrocatalyst prepared in example 1 was weighed, mixed with 0.15mL of 0.5wt.% Nafion solution (obtained by diluting 5wt.% Nafion solution with absolute ethanol, 5wt.% Nafion solution purchased from dupont) and 1.35mL of absolute ethanol, and sonicated for 2 hours to obtain a mixed solution. Dropping the mixed solution on carbon paper to obtain the catalyst with the loading capacity of 1mg cm -2 A cathode of a microbial electrosynthesis system; a three-electrode system is constructed, a platinum mesh electrode with the thickness of 1cm is used as an anode, a reference electrode is a saturated silver/silver chloride electrode, and a closed loop is formed by a cathode, the reference electrode, the anode and an electrochemical workstation. And adding the microbial culture solution as electrolyte, and connecting an electrochemical workstation. Controlling cathode voltage to-0.9V at 30deg.C, sampling 1mL at 0, 10, 30, 60, 120min, and detecting H in electrolyte 2 O 2 Concentration, results are shown in FIG. 5, by-product H 2 O 2 At a concentration of up to only 7. Mu. Mol L -1
As described above, under the above conditions, 1mL was sampled at 0min,10min,30min,1h,2h,3h,5h,24h,48h and 96h, and HO concentration in the electrolyte was measured, and as a result, as shown in FIG. 6, the cumulative production concentration after 96h was only 0.7. Mu. Mol L -1
Since the microorganism itself has a certain resistance to active oxygen species, and part of metabolic activity in the body also requires participation of active oxygen species, the descriptions of related experiments and literature can prove that the concentration of H 2 O 2 And HO. Does not cause any cytotoxicity to microorganisms.
Application example 2
The method comprises the following steps of: a colony was taken from an agar plate, cultured in LB medium for about 12 hours, and then the bacterial solution was centrifuged (7000 rpm,10 minutes) and cultured with microorganismsRepeatedly washing the liquid for three times; redispersing the bacterial liquid to 10 mug ml -1 The gentamicin sulfate is added into a microbial culture solution. Introducing a mixed gas (H) 2 :CO 2 :O 2 =80:15:5) for 48 hours, the cultured Cupriavidus necator was inoculated into a reactor containing 150 ml of the microorganism culture solution.
A three-electrode system microbial electrosynthesis system (same as in application example 1) was constructed, and the reaction apparatus was sterilized at high temperature for use. Using Cupriavidus necator culture solution in application example 1 as electrolyte, connecting electrochemical workstation, inoculating Cupriavidus necator bacteria solution, controlling OD of electrolyte at initial inoculation 600 At 30 deg.c, the cathode voltage is controlled to-0.9V (relative to saturated silver/silver chloride electrode) at 0.2-0.3. CO is introduced every 24 hours 2 15min, and 2mL were sampled. The concentration of metallic nickel in the supernatant was measured after centrifugation of the sample. As a result, as shown in FIG. 7, the concentration of metallic nickel ions was always lower than 0.1mg L -1
Application example 3
A three-electrode system microbial electrosynthesis system (same as in application example 1) was constructed, and the reaction apparatus was sterilized at high temperature for use. Using Cupriavidus necator culture solution in application example 1 as electrolyte, connecting electrochemical workstation, inoculating Cupriavidus necator bacteria solution, controlling OD of electrolyte at initial inoculation 600 At 30 deg.C, the cathode voltages are controlled to be-0.9V, -1.0V, -1.1V and-1.2V (relative to saturated silver/silver chloride electrode), and CO is introduced every 24 hr 2 15min, and 2mL were sampled.
The concentration of poly-beta-hydroxybutyrate in the precipitate was measured after centrifugation of the sample and the results are shown in FIG. 8. The cathode voltage (absolute value) is increased, the hydrogen yield is increased, the accumulation speed of poly beta-hydroxybutyrate is increased, and the yield is obviously increased.
The above examples of application are only provided as possible ways of applying the biocompatible hydrogen evolution electrocatalyst, which may be used to construct a dual-chamber microbial electrosynthesis system in addition to the single-chamber microbial electrosynthesis system described above. The above is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto.
While the foregoing embodiments have been described in detail in connection with the embodiments of the invention, it should be understood that the foregoing embodiments are merely illustrative of the invention and are not intended to limit the invention, and any modifications, additions, substitutions and the like made within the principles of the invention are intended to be included within the scope of the invention.

Claims (10)

1. The biocompatible hydrogen evolution electrocatalyst is characterized by comprising 60-80wt% of carbon nano tubes and 20-40wt% of metal nickel nano particles, wherein the metal nickel nano particles are wrapped in the carbon nano tubes with micropore and mesoporous structures.
2. The method for preparing a biocompatible hydrogen evolution electrocatalyst according to claim 1, comprising the steps of:
(1) Respectively dissolving terephthalic acid and nickel acetate in N, N-dimethylformamide to obtain a terephthalic acid solution and a nickel acetate solution, dripping the nickel acetate solution into the terephthalic acid solution, heating, stirring, reacting, collecting a solid product, washing and drying to obtain the Ni-PTA metal organic framework;
(2) Calcining the Ni-PTA metal organic frame obtained in the step (1) at a high temperature in an inert gas atmosphere, cooling to obtain black powder, and pickling to obtain the biocompatible hydrogen evolution electrocatalyst.
3. The method for preparing a biocompatible hydrogen evolution electrocatalyst according to claim 2, wherein in step (1), the concentration of the terephthalic acid solution is 0.1 to 0.3mol L -1 The method comprises the steps of carrying out a first treatment on the surface of the The concentration of the nickel acetate solution is 0.1-0.3mol L -1 The method comprises the steps of carrying out a first treatment on the surface of the The volume ratio of the terephthalic acid solution to the nickel acetate solution is 1:1-2.
4. The method for preparing a biocompatible hydrogen evolution electrocatalyst according to claim 2, wherein in step (1), the conditions of the heating and stirring reaction are 80 to 120 ℃ for 2 to 8 hours.
5. The method for preparing a biocompatible hydrogen evolution electrocatalyst according to claim 2, wherein in step (2), the inert gas atmosphere is a nitrogen atmosphere, the calcination temperature is 700 to 900 ℃, and the calcination time is 2 to 3 hours.
6. The method for preparing a biocompatible hydrogen evolution electrocatalyst according to claim 2, wherein in step (2), the rate of temperature rise by high temperature calcination is from 5 to 10 ℃ for min -1
7. The method for preparing a biocompatible hydrogen evolution electrocatalyst according to claim 2, wherein in step (2), sulfuric acid is used for pickling for 12 to 24 hours.
8. Use of the biocompatible hydrogen evolution electrocatalyst according to claim 1 for the electrocatalytic conversion of carbon dioxide by microorganisms.
9. The use of a biocompatible hydrogen evolution electrocatalyst according to claim 8 for the electrocatalytic conversion of carbon dioxide by microorganisms, wherein the biocompatible hydrogen evolution electrocatalyst is supported on a cathode using a microbial electrosynthesis system to promote the immobilization of CO by aerobic or anaerobic microorganisms 2 And converts it into a high value added product.
10. A method for the electrocatalytic conversion of carbon dioxide by microorganisms, comprising the steps of: constructing a three-electrode system, taking a carbon electrode loaded with the biocompatible hydrogen evolution electrocatalyst according to claim 1 as a cathode, taking Ag/AgCl as a reference electrode, taking a platinum electrode as an anode, forming a closed loop by the cathode, the reference electrode, the anode and an electrochemical workstation, taking an aerobic microorganism culture solution as electrolyte, connecting the electrochemical workstation, inoculating aerobic microorganisms, and controlling the OD of the electrolyte during initial inoculation 600 Is 0.2 to 0.3, runs under the cathode voltage of minus 0.9 to minus 1.2V at room temperature, and uses CO 2 Converting into a high added value product.
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